EP0783019B1 - Thermoplastic compositions with improved X-ray contrast - Google Patents

Thermoplastic compositions with improved X-ray contrast Download PDF

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Publication number
EP0783019B1
EP0783019B1 EP96118830A EP96118830A EP0783019B1 EP 0783019 B1 EP0783019 B1 EP 0783019B1 EP 96118830 A EP96118830 A EP 96118830A EP 96118830 A EP96118830 A EP 96118830A EP 0783019 B1 EP0783019 B1 EP 0783019B1
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weight
mixtures
thermoplastic
styrene
polymer
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German (de)
French (fr)
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EP0783019A1 (en
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Michael Dr. Bödiger
Herbert Dr. Eichenauer
Heinrich Dr. Alberts
Dieter Dr. Wittmann
Thomas Dr. Eckel
Peter Dr. Krüger
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function

Definitions

  • the invention relates to mixtures of thermoplastic polymers and very finely divided inorganic substances, in addition to an improved X-ray contrast have good mechanical properties.
  • plastic parts in the human body e.g. swallowed Plastic toys or plastic particles injected by accidents in the tissue, is gaining in importance.
  • the x-ray contrast media also support ultrasound diagnostics and computer tomography.
  • BaSO 4 can be worked in afterwards.
  • EP-A 419 927 describes thermoplastic molding compositions made from polyalkylene terephthalate, special barium sulfate, particulate graft polymers and optionally reinforcing agents, which have improved heat resistance and toughness.
  • EP-A 416 407 describes thermoplastic molding compositions made of polycarbonate, polyalkylene terephthalate, special barium sulfate and optionally elastomers with improved heat resistance and toughness.
  • US-A 5,207,703 describes medical devices and generally mentions that barium sulfate can be used for X-rays.
  • the toughness is significantly less deteriorated, heat resistance and petrol resistance are increased and the transparency largely preserved.
  • the x-ray contrast is that of the invention Molding compounds compared to those filled with conventional minerals Molding compounds sharper.
  • all fillers for example pigments, dyes, fibers, are suitable for increasing the X-ray contrast, provided that they contain elements whose atomic number is at least 5, preferably at least 15 and particularly preferably at least 25 above that of the element with the highest atomic number in the plastic used, and their average particle diameter is 0.1 to 100 nm. Finely divided BaSO 4 is particularly suitable.
  • Polymers are particularly suitable if none are in the processed solid state have crystalline areas, i.e. are completely amorphous.
  • the "amorphous" is the one in L.H. Sparrow: Indroduction to Physical Polymer Science, J. Wiley & Sons, 1986, p. 123 understood the polymer state described.
  • Vinyl polymers A.1 are copolymers of styrene on the one hand, ⁇ -methylstyrene, nucleus-substituted styrene or mixtures (A.1.1) and on the other hand acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleimide or mixtures (A.1.2).
  • copolymers preferably contain 50 to 98% by weight of A.1.1 and 50 to 2% by weight of A.1.2.
  • Particularly preferred copolymers A.1 are those made from styrene, acrylonitrile and optionally methyl methacrylate, from ⁇ -methylstyrene, acrylonitrile and optionally Methyl methacrylate and from styrene, ⁇ -methylstyrene, acrylonitrile and optionally Methyl methacrylate.
  • the best known are styrene-acrylonitrile copolymers which can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the copolymers A.1 preferably have molecular weights M w (weight average, determined by light scattering or sedimentation) from 15,000 to 200,000.
  • copolymers A.1 are statistically based Copolymers of styrene and maleic anhydride, e.g. through a continuous Bulk or solution polymerization with incomplete sales the corresponding monomer can be prepared. Your composition can be varied within wide limits. They preferably contain 5 up to 25% by weight of maleic anhydride units.
  • these polymers can also contain nucleus-substituted styrenes, such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes, such as ⁇ -methylstyrene.
  • nucleus-substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes, such as ⁇ -methylstyrene.
  • Preferred polymers A.2 are partially crosslinked and have gel contents of over 20% by weight, preferably over 40% by weight, in particular over 60% by weight.
  • Preferred graft polymers A.2 are e.g. with styrene and / or acrylonitrile and / or methacrylates grafted polybutadienes, Butadiene / styrene copolymers and acrylate rubbers; i.e.
  • Methacrylic esters ⁇ are esters of Methacrylic acid and monohydric alcohols with 1 to 18 carbon atoms. Especially methyl methacrylate, ethyl methacrylate, propyl methacrylate are preferred, and t-butyl methacrylate.
  • the butadiene polymer can ⁇ in addition to butadiene up to 50 wt .-%, based on ⁇ , residues of other ethylenically unsaturated monomers such as styrene, acrylonitrile, C 1 -C 4 alkyl esters or acrylic or methacrylic acid (such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate ), Vinyl ester and / or vinyl ether).
  • Polybutadiene is preferred.
  • the graft monomers are not used in the graft polymerization fully polymerized onto the graft base; close according to the invention Graft polymers A.2 but a product by polymerization of the Graft monomers can be obtained in the presence of the graft base.
  • the degree of grafting G is the weight ratio of grafted grafted monomers to the graft base (dimensionless number).
  • the average particle diameter d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-796).
  • the acrylate rubbers ⁇ of the polymers A.2 are preferably polymers of acrylic acid alkyl esters, optionally with up to 40% by weight, based on ⁇ , of other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include C 1 -C 8 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen C 1 -C 8 alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.
  • Monomers with more than one polymerizable double bond can be used for crosslinking be copolymerized.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms or saturated polyols 2 to 4 OH groups and 2 to 20 C atoms, e.g. Ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as Di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, Diallyl phthalate and heterocyclic compounds containing at least 3 have ethylenically unsaturated groups.
  • Cyclic monomers are particularly preferred crosslinking monomers Triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-triazine, Triallylbenzenes.
  • the amount of the crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft base ⁇ .
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which can optionally be used in addition to the acrylic acid esters to prepare the graft base are, for example, acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl-C 1 -C 6 -alkyl ethers, methyl methacrylate, butadiene.
  • Preferred acrylate rubbers as the graft base ⁇ are emulsion polymers which have a gel content of at least 60% by weight.
  • Suitable graft bases according to A.2.2 include silicone rubbers graft-active sites as described in DE-OS 37 04 657, DE-OS 37 04 655, DE-OS 36 31 540 and DE-OS 36 31 539 are described.
  • the gel content of the graft base A.2.2 is at 25 ° C in dimethylformamide determined (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg-Thieme-Verlag, Stuttgart 1977).
  • the graft polymers A. 2 can by known methods such as bulk, Suspension, emulsion or bulk suspension processes can be produced.
  • thermoplastic polymers A can also be polycondensates which are caused by Polycondensation has been prepared from at least one reactive compound are preferably polycarbonates and / or polyester.
  • Polycarbonates suitable according to the invention are both homopolycarbonates and also copolycarbonates.
  • A can also be a mixture of the thermoplastic defined above Be polycarbonates.
  • Polycarbonates can be made in a known manner from diphenols with phosgene Phase boundary process or with phosgene according to the process in homogeneous Phase, the so-called pyridine process, the molecular weight in a known manner by a corresponding amount of known Chain breakers can be adjusted.
  • Suitable chain terminators are e.g. Phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) phenol according to DE-OS 2 842 005 (Le A 19 006) or monoalkylphenol or dialkylphenol with a total of 8-20 carbon atoms in the alkyl substituents according to German patent application P 3 506 472.2, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethyl-heptyl) phenol and 4- (3,5-dimethyl-heptyl) phenol.
  • long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) phenol according to DE-OS 2 842
  • the amount of chain terminators is generally between 0.5 and 10 mol%, based on the sum of the diphenols (I) used in each case.
  • the polycarbonates A suitable according to the invention have average molecular weights ( M w, weight average, measured, for example, by ultracentrifugation or scattered light measurement) from 10,000 to 200,000, preferably from 20,000 to 80,000.
  • Suitable diphenols of formula (I) are e.g. Hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
  • Preferred diphenols of the formula (I) are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane.
  • the polycarbonates A which are suitable according to the invention can be prepared in a known manner be branched, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, to three or more than tri-functional connections, e.g. those with three or more than three phenolic groups.
  • preferred polycarbonates are Copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sums on diphenols, on 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
  • the polycarbonates A can be partially or completely aromatic Polyester carbonates to be replaced.
  • Preferred polyesters A are polyalkylene terephthalates. These are reaction products aromatic dicarboxylic acids (or their reactive derivatives, e.g. Dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.
  • Preferred polyalkylene terephthalates can be obtained from terephthalic acids (or their reactive derivatives) and aliphatic and cycloaliphatic diols with 2 produce up to 10 carbon atoms using known methods (plastics manual), Volume VIII, p. 695 ff, Carl Hanser Verlag, Kunststoff 1973).
  • Preferred polyalkylene terephthalates contain 80 to 100, preferably 90 to 100 mol%, based on the dicarboxylic acid component, terephthalic acid residues and 80 to 100, preferably 90 to 100 mol%, based on the diol component, Ethylene glycol and / or 1,4-butanediol residues.
  • residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or contain aliphatic dicarboxylic acids with 4 to 12 carbon atoms such as residues of Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, Succinic, adipic, sebacic, azelaic or cyclohexanediacetic acid.
  • Ethylene glycol and / or 1,4-butanediol residues are 0 to 20 mol% of other aliphatic Diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 12 carbon atoms included, e.g.
  • the polyalkylene terephthalates can be 3- or by incorporating relatively small amounts 4-valent alcohols or 3- or 4-based carboxylic acids, as described in DE-OS 1 900 270 and US Pat. No. 3,692,744 are described.
  • preferred branching agents are trimesic acid, trimellitic acid, Trimethylolethane and propane and pentraerythritol. It is advisable not to exceed 1 mol% of the branching agent, based on the acid component use.
  • Polyalkylene terephthalates which consist solely of terephthalic acid are particularly preferred (or their reactive derivatives, e.g. their dialkyl esters) and ethanediol and / or 1,4-butanediol have been prepared, and mixtures thereof.
  • Preferred polyalkylene terephthalates are also copolyesters which consist of at least two of the above diols are prepared; particularly preferred copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates. Can in the copolyesters the various diol residues in the form of blocks or statistically distributed available.
  • the polyalkylene terephthalates generally have an intrinsic viscosity of 0.4 to 1.4 dl / g, preferably 0.5 to 1.3 dl / g, in particular 0.6 to 1.2 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 part by weight) at 25 ° C.
  • Component B comprises very finely divided inorganic materials made of BaSO 4 , TiN, TiO 2 , TaC, SiC, WC, WO 3 , ZrO 2 , iron oxides. Mixtures and doped compounds can also be used. BaSO 4 , TiO 2 , ZrO 2 are particularly preferred, BaSO 4 is very particularly preferred.
  • thermoplastics A are incorporated, for example by direct kneading or extrusion of plastic A and the finely divided inorganic powders B.
  • Preferred methods are the production of a Masterbatch, e.g. in flame retardant additives and other additives, monomers or solvents, or the co-precipitation of an aqueous emulsion and the finely divided inorganic materials.
  • the production of very finely divided inorganic materials in the presence of aqueous polymer systems e.g. ABS-latexes. It works Incorporation without separate processing of the finely divided inorganic materials into the thermoplastic molding compounds.
  • the average particle diameter (d 50 ) is 0.1 to 100 nm, preferably 0.1 to 50 nm, particularly preferably 0.1 to 30 nm.
  • Particle size and particle diameter always mean the average particle diameter d 50 . This can be determined, for example, by ultracentrifuge measurements according to W. Scholtan et al., Kolloid-Z and Z. Polymer 250 (1972), pp. 782 to 796 (preferably in the case of dispersions) or by transmission electron microscopy (TEM) (preferably in the case of thermoplastic molding compositions).
  • TEM transmission electron microscopy
  • the molding compositions according to the invention contain at least one thermoplastic polymer based on unsaturated monomers containing at least one styrene (derivative) or at least one polycondensate of bifunctional reactive compounds or mixtures thereof, and at least one inorganic material with an average particle diameter (d 50 ) of 0.1 to 100 nm, preferably 1 to 50 nm, particularly preferably 1 to 30 nm.
  • Preferred amounts of the inorganic very finely divided materials are 0.1 to 50% by weight, particularly preferably 0.1 to 30% by weight, very particularly preferably 0, 1 to 10 wt .-% (based on thermoplastic molding compositions A).
  • all usual fillers e.g. Suitable pigments, dyes, fibers that contain elements, their atomic number above that of the element with the highest atomic number in the inserted Plastic is and their average particle diameter in the invention Area.
  • the molding compositions can be customary Additives such as pigments, fillers, stabilizers, antistatic agents, lubricants, mold release agents, Contain flame retardants, provided they do not reduce the toughness.
  • BaSO 4 Barifine BF20, Nordmann + Rassmann, particle size approx. 25 ⁇ m
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the average particle size of the BaSO 4 in the polymer is approx. 25 ⁇ m
  • the BaSO 4 concentration is 10% by weight (polymer P1).
  • the production of injection molded parts for testing the properties of the Polymers P1, P2, P2A, P3, P4, P5 and P6 are made by premixing the components, ("Dry Blending") and subsequent direct processing. This will be The mixture melted and sprayed directly.
  • the processing temperature is 250 ° C, the tool temperature is 70 ° C.
  • Very fine BaSO 4 is produced in-situ in the presence of a SAN latex.
  • SAN latex solid: 43.55% by weight
  • 22.2 g of sodium dodecyl sulfate (SDS) in 380 g of water are added dropwise within 50 minutes.
  • 244.7 g of Na 2 SO 4 in 4,600 g of water are then added dropwise over the course of 2.5 h.
  • 367 g of Ba (acetate) 2 in 4,000 g of water are then added over a period of 2.5 hours at a stirring speed of 430 rpm.
  • Barium is deficient compared to sulfate.
  • a precipitation liquor consisting of 11.5 water, 115 ml conc. Acetic acid and 230 g of Epsom salt (MgSO 4 * 7H 2 O) submitted.
  • the liquor is heated to 95 ° C.
  • the dispersion is added with stirring, heated to 100 ° C. and left at this temperature for 10 min.
  • the precipitate is cooled by adding water and washed sulfate-free on a plan filter.
  • the resulting powder is dried at 70 ° C (polymer P2).
  • the average particle diameter of BaSO 4 in the polymer is approx. 40 nm.
  • the polymer P2 is mixed with an ABS graft powder and sprayed off.
  • the BaSO 4 content in the end product is 10% by weight.
  • the average particle size of BaSO 4 in the polymer is approx. 40 nm (polymer P2A).
  • BaSO 4 Barifine BF 20, Nordmann + Rassmann, average particle diameter approx. 25 ⁇ m
  • SAN acrylonitrile-styrene copolymer
  • the average particle diameter of the BaSO 4 in the polymer is approx. 25 ⁇ m
  • the BaSO 4 concentration is 10% by weight (polymer P3).
  • the polymer matrix is transparent without BaSO 4 .
  • the average particle diameter of the BaSO 4 in the polymer is approx. 40 nm, the BaSO 4 concentration is 10% by weight.
  • the polymer matrix is transparent without BaSO 4 .
  • ABS graft powder polymer P5
  • the polymer composition of the polymers P1, P2A and P5 is identical and has the following composition:
  • ABS acrylonitrile-butadiene-styrene polymers
  • SAN is a thermoplastic resin consisting of 28% by weight acrylonitrile and 72% by weight styrene.
  • SAN can be made by emulsion polymerization (SAN latex) or bulk process.
  • the L value of the SAN resin used is 60.
  • ABS graft powder is made by emulsion polymerization of styrene and acrylonitrile in the presence of an aqueous polybutadiene emulsion (polybutadiene base) manufactured. Styrene and acrylonitrile are applied to the polybutadiene particles grafted. As is known, the grafting is not complete, so that in addition to grafted SAN there is also free SAN in the ABS graft powder.
  • the particle size of the polybutadiene base is 0.4 ⁇ m.
  • the polymer composition of the polymers P3, P4 and P6 is identical and has the following composition:
  • the styrene-acrylonitrile polymer is a transparent, thermoplastic resin consisting of 28% by weight of acrylonitrile and 72% by weight of styrene.
  • SAN can be made by emulsion polymerisation (SAN latex) or mass processing.
  • the L value of the SAN resin used is 60.
  • thermoplastic molding compounds are sprayed off and the following tests are carried out:
  • Injection molding is used to produce rods measuring 80 x 10 x 4 mm 3 , on which the notched impact strength is measured at room temperature using the ISO 180 1 A method.
  • Injection molding is used to produce rods measuring 80 x 10 x 4 mm 3 , on which the Vicat softening temperature (VST) is determined in accordance with ISO 306.
  • VST Vicat softening temperature
  • the gasoline resistance (stress crack behavior) is examined on the flat bars 80 x 10 x 4 mm 3 according to DIN 53 449/3.
  • the test specimens were pre-stretched using a circular template and stored in the fuel simulator for 5 minutes at 23 ° C.
  • the stress crack behavior was assessed via the crack formation or the break.
  • the pre-stretch which breaks after 5 minutes, is shown in the following table.
  • the notched impact strength at 10% by weight of finely divided BaSO 4 shows an acceptable level for ABS, while the notched impact strength drops drastically with 10% by weight of commercially available BaSO 4 (decrease to approx. 1/5 of the initial level). Even small amounts of the commercially available BaSO 4 (1.5% by weight) lead to a drop in toughness to approximately half of the initial level.
  • the gasoline resistance, expressed in the edge fiber stretching to breakage, is significantly improved when adding finely divided BaSO 4 .
  • the addition of conventional BaSO 4 does not improve this property.
  • Polymer P5 shows no X-ray contrast in the X-ray experiment.
  • Polymer P1 shows a clear, somewhat diffuse X-ray contrast under the same conditions, while the polymer P2A according to the invention under the same conditions shows a clear, sharp X-ray contrast.
  • the transparency of SAN is compared after the addition of commercially available BaSO 4 and finely divided BaSO 4 .
  • the turbidity is measured in accordance with ASTM D 1003.
  • the thickness of the test specimen is 2 mm.
  • the results of the tests are summarized in the following table: polymer BaSO 4 [% by weight] Very fine BaSO 4 [% by weight] Turbidity [%] P6 - - 34 P3 10 - 89 P4 (according to the invention) - 10 56

Description

Gegenstand der Erfindung sind Mischungen aus thermoplastischen Polymeren und feinstteiligen anorganischen Stoffen, die neben einem verbesserten Röntgenkontrast gute mechanische Eigenschaften aufweisen.The invention relates to mixtures of thermoplastic polymers and very finely divided inorganic substances, in addition to an improved X-ray contrast have good mechanical properties.

Der Nachweis von Kunststoffteilen im menschlichen Körper, z.B. verschlucktem Kunststoffspielzeug oder durch Unfälle im Gewebe eingesprengter Kunststoffpartikel, gewinnt an Bedeutung.The detection of plastic parts in the human body, e.g. swallowed Plastic toys or plastic particles injected by accidents in the tissue, is gaining in importance.

Eine Nachweismethode für Fremdkörper im menschlichen Organismus ist die Röntgendiagnostik. Konventionelle Kunststoffe bestehen zum überwiegenden Anteil aus Elementen mit niedrigen Ordnungszahlen (OZ), wie Kohlenstoff (OZ=6), Wasserstoff (OZ=1), Sauerstoff (OZ=8) und Stickstoff (OZ=7). Die effektiven Ordnungszahlen der Kunststoffe ähneln damit derjenigen des Wassers, so daß die Röntgendichten von konventionellen Kunststoffen und Wasser vergleichbar sind. Daher sind viele konventionelle Kunststoffe im lebenden Gewebe weitgehend röntgenstrahlentransparent.One detection method for foreign bodies in the human organism is X-ray diagnostics. Conventional plastics mostly exist from elements with low atomic numbers (OZ), such as carbon (OZ = 6), Hydrogen (OZ = 1), oxygen (OZ = 8) and nitrogen (OZ = 7). The effective ones The atomic numbers of the plastics thus resemble those of the water, so that the X-ray densities of conventional plastics and water are comparable. Therefore, many conventional plastics are largely used in living tissue X-ray transparent.

Zur Erhöhung der Röntgendichte können Elemente mit höherer Ordnungszahl in den Kunststoffen dienen, z.B. Chlor (OZ = 17) im Polyvinylchlorid, Silicium (OZ = 14) in Silikonen und Fluor (OZ = 9) in Polyfluorcarbon. Bei den konventionellen Kunststoffen weist nur Polyvinylchlorid durch seine hohe Chlorkonzentration einen für die Röntgendiagnostik ausreichenden Kontrast auf (Fortschr. Röntgenstr. 128,6 (1978) 758-762).To increase the x-ray density, elements with a higher atomic number can be in serve the plastics, e.g. Chlorine (OZ = 17) in polyvinyl chloride, silicon (OZ = 14) in silicones and fluorine (OZ = 9) in polyfluorocarbon. Both conventional plastics has only polyvinyl chloride due to its high Chlorine concentration a sufficient contrast for X-ray diagnostics (Progress. Röntgenstr. 128,6 (1978) 758-762).

Eine andere Möglichkeit zur Erhöhung der Röntgendichte ist der Einsatz von Füllstoffen wie Glasfasern (SiO2) oder Farbstoffen bzw. Pigmenten, die aus Elementen mit höherer Ordnungszahl bestehen, z.B. TiO2 (Ti: OZ = 22).Another possibility for increasing the X-ray density is the use of fillers such as glass fibers (SiO 2 ) or dyes or pigments, which consist of elements with a higher atomic number, for example TiO 2 (Ti: OZ = 22).

In der Medizin werden zur Sichtbarmachung von körpereigenen Strukturen mittels Röntgendiagnostik Verbindungen eingesetzt, die Atome mit hoher Ordnungszahl (Röntgenkontrastmittel) enthalten, wie BaSO4 (Ba: OZ = 56) oder organische Iodverbindungen (Iod: OZ = 53). Die Röntgenkontrastmittel unterstützen auch die Ultraschalldiagnostik und die Computertomographie. In medicine, X-ray diagnostics uses compounds that contain atoms with a high atomic number (X-ray contrast media), such as BaSO 4 (Ba: OZ = 56) or organic iodine compounds (iodine: OZ = 53), to visualize the body's own structures. The x-ray contrast media also support ultrasound diagnostics and computer tomography.

Um nun verschiedene Kunststoffe, insbesondere solche, ohne Elemente mit höherer Ordnungszahl (OZ > 8), röntgenologisch effektiv abzubilden, kann man z.B. nachträglich BaSO4 einarbeiten.In order to be able to effectively X-ray various plastics, in particular those without elements with a higher atomic number (OZ> 8), BaSO 4 can be worked in afterwards.

Arbeitet man BaSO4 in Polymere ein, so wird erwartungsgemäß der Röntgenkontrast gegenüber dem ungefüllten Polymeren deutlich verbessert. Konventionelle Füllstoffe verschlechtern jedoch die Zähigkeit drastisch und sind für transparente Polymere völlig ungeeignet (Trübung).If BaSO 4 is incorporated into polymers, the X-ray contrast is expected to be significantly improved compared to the unfilled polymer. Conventional fillers, however, drastically reduce toughness and are completely unsuitable for transparent polymers (cloudiness).

EP-A 419 927 beschreibt thermoplastische Formmassen aus Polyalkylenterephthalat, speziellem Bariumsulfat, teilchenförmigen Pfropfpolymerisaten und gegebenenfalls Verstärkungsmitteln, die eine verbesserte Wärmeformbeständigkeit und Zähigkeit aufweisen. EP-A 416 407 beschreibt thermoplastische Formmassen aus Polycarbonat, Polyalkylenterephthalat, speziellem Bariumsulfat und gegebenenfalls Elastomeren mit verbesserter Wärmeformbeständigkeit und Zähigkeit.
US-A 5,207,703 beschreibt medizinische Geräte und erwähnt allgemein, dass Bariumsulfat für Röntgenaufnahmen eingesetzt werden kann.EP-A 419 927 describes thermoplastic molding compositions made from polyalkylene terephthalate, special barium sulfate, particulate graft polymers and optionally reinforcing agents, which have improved heat resistance and toughness. EP-A 416 407 describes thermoplastic molding compositions made of polycarbonate, polyalkylene terephthalate, special barium sulfate and optionally elastomers with improved heat resistance and toughness.
US-A 5,207,703 describes medical devices and generally mentions that barium sulfate can be used for X-rays.

Es wurde gefunden, daß beim Einsatz von speziellen feinstteiligen Stoffen zur Erzielung eines Röntgenkontrastes im Vergleich zu entsprechenden konventionellen Stoffen die Zähigkeit deutlich weniger verschlechtert wird, Wärmeformbeständigkeit und Benzinbeständigkeit erhöht werden und die Transparenz weitgehend erhalten bleibt. Darüber hinaus ist der Röntgenkontrast der erfindungsgemäßen Formmassen gegenüber den mit konventionellen Mineralien gefüllten Formmassen schärfer.It has been found that when using special, very finely divided substances for Achieving an x-ray contrast in comparison to corresponding conventional ones Fabrics the toughness is significantly less deteriorated, heat resistance and petrol resistance are increased and the transparency largely preserved. In addition, the x-ray contrast is that of the invention Molding compounds compared to those filled with conventional minerals Molding compounds sharper.

Erfindungsgemäß sind zur Erhöhung des Röntgenkontrastes alle Füllstoffe, z.B. Pigmente, Farbstoffe, Fasern, geeignet, sofern sie Elemente enthalten, deren Ordnungszahl mindestens 5, vorzugsweise mindestens 15 und besonders bevorzugt mindestens 25 über denen des Elementes mit der höchsten Ordnungszahl im eingesetzten Kunststoff liegt, und ihr mittlerer Teilchendurchmesser 0,1 bis 100 nm beträgt. Besonders geeignet ist feinstteiliges BaSO4.According to the invention, all fillers, for example pigments, dyes, fibers, are suitable for increasing the X-ray contrast, provided that they contain elements whose atomic number is at least 5, preferably at least 15 and particularly preferably at least 25 above that of the element with the highest atomic number in the plastic used, and their average particle diameter is 0.1 to 100 nm. Finely divided BaSO 4 is particularly suitable.

Gegenstand der Erfindung sind thermoplastische Formmassen bestehend im wesentlichen aus

  • A) einem thermoplastischen Polymer ausgewählt aus
  • A.1) Copolymerisate aus einerseits Styrol, ∝-Methylstyrol, kernsubstituiertem Styrol oder Mischungen (A.1.1) und andererseits Acrylnitril, Methacrylnitril, Methylmethacrylat, Maleinsäureanhydrid, N-substituiertes Maleinimid oder Mischungen (A.1.2)
  • A.2) ein Pfropfpolymerisat von
  • A.2.1 5 bis 95 Gew.-Teilen, einer Mischung aus
  • A.2.1.1. 50 bis 95 Gew.-Teilen Styrol, α-Methylstyrol, halogen- oder methylkernsubstituierten Styrolen, Methylmethacrylat oder Mischungen dieser Verbindungen und
  • A.2.1.1 5 bis 50 Gew.-Teilen Acrylnitril, Methacrylnitril, Methylmethacrylat, Maleinsäureanhydrid, C1-C4-alkyl- bzw. phenyl-N-substituierten Maleinimiden oder Mischungen dieser Verbindungen auf
  • A.2.2 5 bis 95 Gew.-Teile Kautschuk-Polymerisat mit einer Glasübergangstemperatur von - 10 °C.
    • oder Mischungen von A.1) und A.2), und gegebenenfalls thermoplastischem Polycarbonat,
       und
  • B) 0,1 bis 50 Gew.-% (bezogen auf A) anorganischen Stoff mit einem mittleren Teilchendurchmesser von 0,1 bis 100 nm ausgewählt aus BaSO4, TiN, TiO2, TaC, SiC, WC, WO3, ZrO2 und Eisenoxiden, Mischungen hier aus oder dotierte Verbindungen.
    •  The invention relates to thermoplastic molding compositions consisting essentially of
  • A) a thermoplastic polymer selected from
  • A.1) Copolymers of styrene, ∝-methylstyrene, nucleus-substituted styrene or mixtures (A.1.1) and acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleimide or mixtures (A.1.2)
  • A.2) a graft polymer of
  • A.2.1 5 to 95 parts by weight, a mixture of
  • A.2.1.1. 50 to 95 parts by weight of styrene, α-methylstyrene, halogen- or methyl-substituted styrenes, methyl methacrylate or mixtures of these compounds and
  • A.2.1.1 5 to 50 parts by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, C 1 -C 4 alkyl- or phenyl-N-substituted maleimides or mixtures of these compounds
  • A.2.2 5 to 95 parts by weight of rubber polymer with a glass transition temperature of -10 ° C.
    • or mixtures of A.1) and A.2), and optionally thermoplastic polycarbonate,
    and
  • B) 0.1 to 50% by weight (based on A) of inorganic substance with an average particle diameter of 0.1 to 100 nm selected from BaSO 4 , TiN, TiO 2 , TaC, SiC, WC, WO 3 , ZrO 2 and iron oxides, mixtures here of or doped compounds.

    • Thermoplastische Polymere AThermoplastic polymers A

    Besonders geeignet sind Polymere, die im verarbeiteten festen Zustand keine kristallinen Bereiche aufweisen, d.h. völlig amorph sind.Polymers are particularly suitable if none are in the processed solid state have crystalline areas, i.e. are completely amorphous.

    Als "amorph" wird hierbei der in L.H. Sperling: Indroduction to Physical Polymer Science, J. Wiley & Sons, 1986, S. 123 beschriebene Polymerzustand verstanden.The "amorphous" is the one in L.H. Sparrow: Indroduction to Physical Polymer Science, J. Wiley & Sons, 1986, p. 123 understood the polymer state described.

    Thermoplastische Polymere sind ausgewählt aus

    • kautschukfreien Vinylpolymerisaten (A.1)
    • kautschukhaltigen Vinylpolymerisaten, z.B. Pfropfpolymerisaten von Vinylmonomeren auf einen Kautschuk (A.2)
    • Mischungen aus kautschukfreien (A.1) und kautschukhaltigen (A.2) Vinylpolymerisaten.
    Thermoplastic polymers are selected from
    • rubber-free vinyl polymers (A.1)
    • rubber-containing vinyl polymers, for example graft polymers of vinyl monomers on a rubber (A.2)
    • Mixtures of rubber-free (A.1) and rubber-containing (A.2) vinyl polymers.

    Vinylpolymerisate A.1 sind Copolymerisate aus einerseits Styrol, ∝-Methylstyrol, kernsubstituiertem Styrol oder Mischungen (A.1.1) und andererseits Acrylnitril, Methacrylnitril, Methylmethacrylat, Maleinsäureanhydrid, N-substituiertes Maleinimid oder Mischungen (A.1.2).Vinyl polymers A.1 are copolymers of styrene on the one hand, ∝-methylstyrene, nucleus-substituted styrene or mixtures (A.1.1) and on the other hand acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleimide or mixtures (A.1.2).

    Bevorzugt enthalten diese Copolymerisate 50 bis 98 Gew.-% A.1.1 und 50 bis 2 Gew.-% A.1.2. These copolymers preferably contain 50 to 98% by weight of A.1.1 and 50 to 2% by weight of A.1.2.

    Besonders bevorzugte Copolymerisate A.1 sind solche aus Styrol, Acrylnitril und gegebenenfalls Methylmethacrylat, aus α-Methylstyrol, Acrylnitril und gegebenenfalls Methylmethacrylat sowie aus Styrol, α-Methylstyrol, Acrylnitril und gegebenenfalls Methylmethacrylat.Particularly preferred copolymers A.1 are those made from styrene, acrylonitrile and optionally methyl methacrylate, from α-methylstyrene, acrylonitrile and optionally Methyl methacrylate and from styrene, α-methylstyrene, acrylonitrile and optionally Methyl methacrylate.

    Die bekanntesten sind Styrol-Acrylnitril-Copolymerisate, die durch radikalische Polymerisation, insbesondere durch Emulsions-, Suspensions-, Lösungs- oder Massepolymerisation hergestellt werden können. Die Copolymerisate A.1 besitzen vorzugsweise Molekulargewichte M w (Gewichtsmittel, ermittelt durch Lichtstreuung oder Sedimentation) von 15.000 bis 200.000.The best known are styrene-acrylonitrile copolymers which can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The copolymers A.1 preferably have molecular weights M w (weight average, determined by light scattering or sedimentation) from 15,000 to 200,000.

    Weitere besonders bevorzugte Copolymerisate A.1 sind statistisch aufgebaute Copolymerisate aus Styrol und Maleinsäureanhydrid, die z.B. durch eine kontinuierliche Masse- oder Lösungspolymerisation bei unvollständigen Umsätzen aus dem entsprechenden Monomeren hergestellt werden können. Ihre Zusammensetzung kann innerhalb weiter Grenzen variiert werden. Bevorzugt enthalten sie 5 bis 25 Gew.-% Maleinsäureanhydrideinheiten.Other particularly preferred copolymers A.1 are statistically based Copolymers of styrene and maleic anhydride, e.g. through a continuous Bulk or solution polymerization with incomplete sales the corresponding monomer can be prepared. Your composition can be varied within wide limits. They preferably contain 5 up to 25% by weight of maleic anhydride units.

    Anstelle von Styrol können diese Polymerisate auch kernsubstituierte Styrole, wie p-Methylstyrol, Vinyltoluol, 2,4-Dimethylstyrol und andere substituierte Styrole, wie α-Methylstyrol, enthalten.Instead of styrene, these polymers can also contain nucleus-substituted styrenes, such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes, such as α-methylstyrene.

    Bevorzugte Polymerisate A.2 sind partiell vernetzt und besitzen Gelgehalte von über 20 Gew.-%, vorzugsweise über 40 Gew.-%, insbesondere über 60 Gew.-%.Preferred polymers A.2 are partially crosslinked and have gel contents of over 20% by weight, preferably over 40% by weight, in particular over 60% by weight.

    Kautschukartige Vinylpolymerisate A.2 sind Pfropfpolymerisate aus:

    A.2.1
    5 bis 95, vorzugsweise 30 bis 80 Gew.-Teilen, einer Mischung aus
    A.2.1.1
    50 bis 95 Gew.-Teilen Styrol, α-Methylstyrol, halogen- oder methylkernsubstituierten Styrolen, Methylmethacrylat oder Mischungen dieser Verbindungen und
    A.2.1.2
    5 bis 50 Gew.-Teilen Acrylnitril, Methacrylnitril, Methylmethacrylat, Maleinsäuranhydrid, C1-C4-alkyl- bzw. phenyl-N-substituierten Maleinimiden oder Mischungen dieser Verbindungen auf
    A.2.2
    5 bis 95, vorzugsweise 20 bis 70 Gew.-Teile Kautschuk-Polymerisat mit einer Glasübergangstemperatur unter -10°C.
    Rubber-like vinyl polymers A.2 are graft polymers of:
    A.2.1
    5 to 95, preferably 30 to 80 parts by weight of a mixture of
    A.2.1.1
    50 to 95 parts by weight of styrene, α-methylstyrene, halogen- or methyl-substituted styrenes, methyl methacrylate or mixtures of these compounds and
    A.2.1.2
    5 to 50 parts by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, C 1 -C 4 alkyl- or phenyl-N-substituted maleimides or mixtures of these compounds
    A.2.2
    5 to 95, preferably 20 to 70 parts by weight of rubber polymer with a glass transition temperature below -10 ° C.

    Bevorzugte Pfropfpolymerisate A.2 sind z.B. mit Styrol und/oder Acrylnitril und/oder Methacrylaten gepfropfte Polybutadiene, Butadien/Styrol-Copolymerisate und Acrylatkautschuke; d.h. Copolymerisate der in der DE-OS 1 694 173 (= US-PS 3 564 077) beschriebenen Art; mit Methacrylsäurealkylestern, Vinylacetat, Acrylnitril, Styrol und/oder Alkylstyrolen gepfropfte Polybutadiene, Butadien/Styrol- oder Butadien/Acrylnitril-Copolymerisate, Polyisobutene oder Polyisoprene, wie sie z.B. in der DE-OS 2 348 377 (= US-PS 3 919 353) beschrieben sind.Preferred graft polymers A.2 are e.g. with styrene and / or acrylonitrile and / or methacrylates grafted polybutadienes, Butadiene / styrene copolymers and acrylate rubbers; i.e. Copolymers of in DE-OS 1 694 173 (= US-PS 3 564 077) described type; With Alkyl methacrylates, vinyl acetate, acrylonitrile, styrene and / or alkylstyrenes grafted polybutadienes, butadiene / styrene or butadiene / acrylonitrile copolymers, Polyisobutenes or polyisoprenes, e.g. in DE-OS 2 348 377 (= US Pat. No. 3,919,353).

    Besonders bevorzugte Polymerisate A.2 sind ABS-Polymerisate, wie sie z.B. in der DE-OS 2 035 390 (= US-PS 3 644 574) und in der DE-OS 2 248 242 (= GB-PS 1 409 275) beschrieben sind.Particularly preferred polymers A.2 are ABS polymers, such as those e.g. in DE-OS 2 035 390 (= US-PS 3 644 574) and in DE-OS 2 248 242 (= GB-PS 1 409 275) are described.

    Besonders bevorzugte Pfropfpolymerisate A.2 sind erhältlich durch Pfropfpolymerisation von

    α.
    10 bis 70, vorzugsweise 15 bis 50, insbesondere 20 bis 40 Gew.-%, bezogen auf Pfropfpolymerisat A.2, von Methacrylsäureestern oder von 10 bis 70, vorzugsweise 15 bis 50, insbesondere 20 bis 40 Gew.-% eines Gemisches aus 10 bis 50, vorzugsweise 20 bis 35 Gew.-%; bezogen auf Gemisch, Acrylnitril, oder Methacrylsäureester und 50 bis 90, vorzugsweise 65 bis 80 Gew.-%, bezogen auf Gemisch, Styrol (als Pfropfauflage A.2.1) auf
    β.
    30 bis 90, vorzugsweise 50 bis 85, insbesondere 60 bis 80 Gew.-%, bezogen auf Pfropfpolymerisat A.2, eines Butadien-Polymerisats mit mindestens 50 Gew.-%, bezogen auf β, Butadienresten (als Pfropfgrundlage A.2.2),
    wobei vorzugsweise der Gelanteil der Pfropfgrundlage β mindestens 40 Gew.-% (in Toluol gemessen), der Pfropfgrad G 0,15 bis 0,55 und der mittlere Teilchendurchmesser d50 des Pfropfpolymerisats A.2 0,05 bis 2 µm, vorzugsweise 0,1 bis 0,6 µm beträgt.Particularly preferred graft polymers A.2 can be obtained by graft polymerization of
    α.
    10 to 70, preferably 15 to 50, in particular 20 to 40% by weight, based on graft polymer A.2, of methacrylic acid esters or from 10 to 70, preferably 15 to 50, in particular 20 to 40% by weight of a mixture of 10 up to 50, preferably 20 to 35% by weight; based on the mixture, acrylonitrile or methacrylic acid ester and 50 to 90, preferably 65 to 80 wt .-%, based on the mixture, styrene (as graft A.2.1)
    β.
    30 to 90, preferably 50 to 85, in particular 60 to 80% by weight, based on graft polymer A.2, of a butadiene polymer with at least 50% by weight, based on β, butadiene residues (as the graft base A.2.2),
    wherein preferably the gel fraction of the graft base β is at least 40% by weight (measured in toluene), the degree of graft G 0.15 to 0.55 and the average particle diameter d 50 of the graft polymer A.2 0.05 to 2 μm, preferably 0, Is 1 to 0.6 µm.

    Methacrylsäureester α sind Ester der Methacrylsäure und einwertiger Alkohole mit 1 bis 18 C-Atomen. Besonders bevorzugt sind Methylmethacrylat, Ethylmethacrylat, Propylmethacrylat, und t-Butylmethacrylat.Methacrylic esters α are esters of Methacrylic acid and monohydric alcohols with 1 to 18 carbon atoms. Especially methyl methacrylate, ethyl methacrylate, propyl methacrylate are preferred, and t-butyl methacrylate.

    Das Butadienpolymerisat β kann neben Butadienresten bis zu 50 Gew.-%, bezogen auf β, Reste anderer ethylenisch ungesättigter Monomerer, wie Styrol, Acrylnitril, C1-C4-Alkylester oder Acryl- oder Methyacrylsäure (wie Methylacrylat, Ethylacrylat, Methylmethacrylat, Ethylmethacrylat), Vinylester und/oder Vinylether) enthalten. Bevorzugt ist Polybutadien.The butadiene polymer can β in addition to butadiene up to 50 wt .-%, based on β, residues of other ethylenically unsaturated monomers such as styrene, acrylonitrile, C 1 -C 4 alkyl esters or acrylic or methacrylic acid (such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate ), Vinyl ester and / or vinyl ether). Polybutadiene is preferred.

    Bei der Pfropfpolymerisation werden die Pfropfmonomeren bekanntlich nicht vollständig auf die Pfropfgrundlage polymerisiert; erfindungsgemäß schließen Pfropfpolymerisate A.2 aber Produkte ein, die durch Polymerisation der Pfropfmonomere in Gegenwart der Pfropfgrundlage gewonnen werden.As is known, the graft monomers are not used in the graft polymerization fully polymerized onto the graft base; close according to the invention Graft polymers A.2 but a product by polymerization of the Graft monomers can be obtained in the presence of the graft base.

    Der Pfropfgrad G ist das Gewichtsverhältnis von aufgepfropften Pfropfmomomeren zur Pfropfgrundlage (Dimensionslose Zahl).The degree of grafting G is the weight ratio of grafted grafted monomers to the graft base (dimensionless number).

    Der mittlere Teilchendurchmesser d50 ist der Durchmesser, oberhalb und unterhalb dessen jeweils 50 Gew.-% der Teilchen liegen. Er kann mittels Ultrazentrifugenmessung (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-796) bestimmt werden.The average particle diameter d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-796).

    Weitere besonders bevorzugte Polymerisate A.2 sind Pfropfpolymerisate aus

    τ.
    20 bis 90 Gew.-%, bezogen auf A.2, Acrylatkautschuk mit einer Glasübergangstemperatur unter -20°C als Pfropfgrundlage A.2.2 und
    δ.
    10 bis 80 Gew.-%, bezogen auf A.2, mindestens eines polymerisierbaren, ethylenisch ungesättigten Monomeren, dessen bzw. deren in Abwesenheit von 1. entstandenen Homo- bzw. Copolymerisate eine Glasübergangstemperatur über 25°C hätten, als Pfropfmonomere A.2.1.
    Other particularly preferred polymers A.2 are graft polymers from
    τ.
    20 to 90 wt .-%, based on A.2, acrylate rubber with a glass transition temperature below -20 ° C as the graft base A.2.2 and
    δ.
    10 to 80% by weight, based on A.2, of at least one polymerizable, ethylenically unsaturated monomer whose or whose homopolymers or copolymers formed in the absence of 1. would have a glass transition temperature above 25 ° C. as graft monomers A.2.1 ,

    Die Acrylatkautschuke τ der Polymerisate A.2 sind vorzugsweise Polymerisate aus Acrylsäurealkylestern, gegebenenfalls mit bis zu 40 Gew.-%, bezogen auf τ, anderen polymerisierbaren, ethylenisch ungesättigten Monomeren. Zu den bevorzugten polymerisierbaren Acrylsäureestern gehören C1-C8-Alkylester, beispielsweise Methyl-, Ethyl-, Butyl-, n-Octyl- und 2-Ethyl-hexylester; Halogenalkylester, vorzugsweise Halogen-C1-C8-alkyl-ester, wie Chlorethylacrylat, sowie Mischungen dieser Monomeren.The acrylate rubbers τ of the polymers A.2 are preferably polymers of acrylic acid alkyl esters, optionally with up to 40% by weight, based on τ, of other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include C 1 -C 8 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen C 1 -C 8 alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.

    Zur Vernetzung können Monomere mit mehr als einer polymerisierbaren Doppelbindung copolymerisiert werden. Bevorzugte Beispiele für vernetzende Monomere sind Ester ungesättigter Monocarbonsäuren mit 3 bis 8 C-Atomen und ungesättigter einwertiger Alkohole mit 3 bis 12 C-Atomen oder gesättigter Polyole mit 2 bis 4 OH-Gruppen und 2 bis 20 C-Atomen, wie z.B. Ethylenglykol-dimethacrylat, Allylmethacrylat; mehrfach ungesättigte heterocyclische Verbindungen, wie z.B. Trivinyl- und Triallylcyanurat; polyfunktionelle Vinylverbindungen, wie Di- und Trivinylbenzole; aber auch Triallylphosphat und Diallylphthalat.Monomers with more than one polymerizable double bond can be used for crosslinking be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms or saturated polyols 2 to 4 OH groups and 2 to 20 C atoms, e.g. Ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as Di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.

    Bevorzugte vernetzende Monomere sind Allylmethacrylat, Ethylenglykoldimethacrylat, Diallylphthalat und heterocyclische Verbindungen, die mindestens 3 ethylenisch ungesättigte Gruppen aufweisen.Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, Diallyl phthalate and heterocyclic compounds containing at least 3 have ethylenically unsaturated groups.

    Besonders bevorzugte vernetzende Monomere sind die cyclischen Monomere Triallylcyanurat, Triallylisocyanurat, Trivinylcyanurat, Triacryloylhexahydro-s-triazin, Triallylbenzole.Cyclic monomers are particularly preferred crosslinking monomers Triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-triazine, Triallylbenzenes.

    Die Menge der vernetzenden Monomeren beträgt vorzugsweise 0,02 bis 5, insbesondere 0,05 bis 2 Gew.-%, bezogen auf die Pfropfgrundlage τ.The amount of the crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft base τ.

    Bei cyclischen vernetzenden Monomeren mit mindestens 3 ethylenisch ungesättigten Gruppen ist es vorteilhaft, die Menge auf unter 1 Gew-% der Pfropfgrundlage τ zu beschränken. For cyclic crosslinking monomers with at least 3 ethylenically unsaturated It is advantageous to reduce the amount to less than 1% by weight of the groups To limit graft base τ.

    Bevorzugte "andere" polymerisierbare, ethylenisch ungesättigte Monomere, die neben den Acrylsäureestern gegebenenfalls zur Herstellung der Pfropfgrundlage dienen können, sind z.B. Acrylnitril, Styrol, α-Methylstyrol, Acrylamide, Vinyl-C1-C6-Alkylether, Methylmethacrylat, Butadien. Bevorzugte Acrylatkautschuke als Pfropfgrundlage τ sind Emulsionspolymerisate, die einen Gelgehalt von mindestens 60 Gew.-% aufweisen.Preferred "other" polymerizable, ethylenically unsaturated monomers which can optionally be used in addition to the acrylic acid esters to prepare the graft base are, for example, acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl-C 1 -C 6 -alkyl ethers, methyl methacrylate, butadiene. Preferred acrylate rubbers as the graft base τ are emulsion polymers which have a gel content of at least 60% by weight.

    Weitere geeignete Pfropfgrundlagen gemäß A.2.2 sind Silikonkautschuke mit pfropfaktiven Stellen, wie sie in DE-OS 37 04 657, DE-OS 37 04 655, DE-OS 36 31 540 und DE-OS 36 31 539 beschrieben werden.Other suitable graft bases according to A.2.2 include silicone rubbers graft-active sites as described in DE-OS 37 04 657, DE-OS 37 04 655, DE-OS 36 31 540 and DE-OS 36 31 539 are described.

    Der Gelgehalt der Pfropfgrundlage A.2.2 wird bei 25°C in Dimethylformamid bestimmt (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I und II, Georg-Thieme-Verlag, Stuttgart 1977).The gel content of the graft base A.2.2 is at 25 ° C in dimethylformamide determined (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg-Thieme-Verlag, Stuttgart 1977).

    Die Pfropfpolymerisate A. 2 können nach bekannten Verfahren wie Masse-, Suspensions-, Emulsions- oder Masse-Suspensionsverfahren hergestellt werden.The graft polymers A. 2 can by known methods such as bulk, Suspension, emulsion or bulk suspension processes can be produced.

    Die thermoplastischen Polymere A können auch Polykondensate sein, die durch Polykondensation aus mindestens einer reaktiven Verbindung hergestellt worden sind vorzugsweise Polycarbonate und/oder Polyester.The thermoplastic polymers A can also be polycondensates which are caused by Polycondensation has been prepared from at least one reactive compound are preferably polycarbonates and / or polyester.

    Bevorzugte Polycarbonate sind solche auf Basis der Diphenole der Formel (I)

    Figure 00090001
    worin

    A
    eine Einfachbindung, ein C1-C5-Alkylen, ein C2-C5-Alkyliden, ein C5-C6-Cycloalkyliden, -S- oder -SO2-,
    B
    Chlor, Brom
    X
    0, 1 oder 2 und
    n
    1 oder 0 sind.
    Preferred polycarbonates are those based on the diphenols of the formula (I)
    Figure 00090001
    wherein
    A
    a single bond, a C 1 -C 5 alkylene, a C 2 -C 5 alkylidene, a C 5 -C 6 cycloalkylidene, -S- or -SO 2 -,
    B
    Chlorine, bromine
    X
    0, 1 or 2 and
    n
    Are 1 or 0.

    Erfindungsgemäß geeignete Polycarbonate sind sowohl Homopolycarbonate als auch Copolycarbonate.Polycarbonates suitable according to the invention are both homopolycarbonates and also copolycarbonates.

    A kann auch eine Mischung der vorstehend definierten thermoplastischen Polycarbonate sein.A can also be a mixture of the thermoplastic defined above Be polycarbonates.

    Polycarbonate können in bekannter Weise aus Diphenolen mit Phosgen nach dem Phasengrenzflächenverfahren oder mit Phosgen nach dem Verfahren in homogener Phase, dem sogenannten Pyridinverfahren, hergestellt werden, wobei das Molekulargewicht in bekannter Weise durch eine entsprechende Menge an bekannten Kettenabbrechern eingestellt werden kann.Polycarbonates can be made in a known manner from diphenols with phosgene Phase boundary process or with phosgene according to the process in homogeneous Phase, the so-called pyridine process, the molecular weight in a known manner by a corresponding amount of known Chain breakers can be adjusted.

    Geeignete Kettenabbrecher sind z.B. Phenol, p-Chlorphenol, p-tert.-Butylphenol oder 2,4,6-Tribromphenol, aber auch langkettige Alkylphenole, wie 4-(1,3-Tetramethylbutyl)-phenol gemäß DE-OS 2 842 005 (Le A 19 006) oder Monoalkylphenol bzw. Dialkylphenol mit insgesamt 8-20 C-Atomen in den Alkylsubstituenten gemäß deutscher Patentanmeldung P 3 506 472.2, wie 3,5-di-tert.-Butylphenol, p-iso-Octylphenol, p-tert.-Octylphenol, p-Dodecylphenol und 2-(3,5-Dimethyl-heptyl)-phenol und 4-(3,5-Dimethyl-heptyl)-phenol.Suitable chain terminators are e.g. Phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) phenol according to DE-OS 2 842 005 (Le A 19 006) or monoalkylphenol or dialkylphenol with a total of 8-20 carbon atoms in the alkyl substituents according to German patent application P 3 506 472.2, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethyl-heptyl) phenol and 4- (3,5-dimethyl-heptyl) phenol.

    Die Menge an Kettenabbrechern beträgt im allgemeinen zwischen 0,5 und 10 Mol-%, bezogen auf die Summe der jeweils eingesetzten Diphenole (I).The amount of chain terminators is generally between 0.5 and 10 mol%, based on the sum of the diphenols (I) used in each case.

    Die erfindungsgemäß geeigneten Polycarbonate A haben mittlere Molekulargewichte (Mw, Gewichtsmittel, gemessen z.B. durch Ultrazentrifugation oder Streulichtmessung) von 10 000 bis 200 000, vorzugsweise von 20 000 bis 80 000.The polycarbonates A suitable according to the invention have average molecular weights ( M w, weight average, measured, for example, by ultracentrifugation or scattered light measurement) from 10,000 to 200,000, preferably from 20,000 to 80,000.

    Geeignete Diphenole der Formel (I) sind z.B. Hydrochinon, Resorcin, 4,4'-Dihydroxydiphenyl, 2,2-Bis-(4-hydroxyphenyl)-propan, 2,4-Bis-(4-hydroxyphenyl)-2-methylbutan, 1,1-Bis-(4-hydroxyphenyl)-cyclohexan, 2,2-Bis-(3-chlor-4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dibrom-4-hydroxyphenyl)-propan.Suitable diphenols of formula (I) are e.g. Hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

    Bevorzugte Diphenole der Formel (I) sind 2,2-Bis-(4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dichlor-4-hydroxyphenyl)-propan und 1,1-Bis-(4-hydroxyphenyl)-cyclohexan. Preferred diphenols of the formula (I) are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane.

    Bevorzugte Diphenole sind auch alkylsubstituierte Dihydroxydiphenylcycloalkane der Formel (II),

    Figure 00110001
    worin

    R1 und R2
    unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom, C1-C8-Alkyl, C5-C6-Cycloalkyl, C6-C10-Aryl, bevorzugt Phenyl, und C7-C12-Aralkyl, bevorzugt Phenyl-C1-C4-Alkyl, insbesondere Benzyl,
    m
    eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5,
    R3 und R4
    für jedes X individuell wählbar, unabhängig voneinander Wasserstoff oder C1-C6-Alkyl
    und
    X
    Kohlenstoff bedeuten,
    mit der Maßgabe, daß an mindestens einem Atom X R3 und R4 gleichzeitig Alkyl bedeuten.
    Preferred diphenols are also alkyl-substituted dihydroxydiphenylcycloalkanes of the formula (II),
    Figure 00110001
    wherein
    R 1 and R 2
    independently of one another hydrogen, halogen, preferably chlorine or bromine, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 6 -C 10 aryl, preferably phenyl, and C 7 -C 12 aralkyl, preferably phenyl C 1 -C 4 alkyl, especially benzyl,
    m
    an integer from 4 to 7, preferably 4 or 5,
    R 3 and R 4
    individually selectable for each X, independently of one another hydrogen or C 1 -C 6 -alkyl
    and
    X
    Carbon mean
    with the proviso that on at least one atom XR 3 and R 4 mean alkyl at the same time.

    Die erfindungsgemäß geeigneten Polycarbonate A können in bekannter Weise verzweigt sein, und zwar vorzugsweise durch den Einbau von 0,05 bis 2,0 Mol-%, bezogen auf die Summe der eingesetzten Diphenole, an drei- oder mehr als dreifunktionellen Verbindungen, z.B. solchen mit drei oder mehr als drei phenolischen Gruppen.The polycarbonates A which are suitable according to the invention can be prepared in a known manner be branched, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, to three or more than tri-functional connections, e.g. those with three or more than three phenolic groups.

    Bevorzugte Polycarbonate sind neben dem Bisphenol-A-Homopolycarbonat die Copolycarbonate von Bisphenol A mit bis zu 15 Mol-%, bezogen auf die Mol-Summen an Diphenolen, an 2,2-Bis-(3,5-dibrom-4-hydroxyphenyl)-propan. In addition to bisphenol A homopolycarbonate, preferred polycarbonates are Copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sums on diphenols, on 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

    Die Polycarbonate A können teilweise oder vollständig durch aromatische Polyestercarbonate ersetzt werden.The polycarbonates A can be partially or completely aromatic Polyester carbonates to be replaced.

    Bevorzugte Polyester A sind Polyalkylenterephthalate. Diese sind Reaktionsprodukte von aromatischen Dicarbonsäuren (oder ihren reaktionsfähigen Derivaten, z.B. Dimethylestern oder Anhydriden) und aliphatischen, cycloaliphatischen oder arylaliphatischen Diolen und Mischungen solcher Reaktionsprodukte.Preferred polyesters A are polyalkylene terephthalates. These are reaction products aromatic dicarboxylic acids (or their reactive derivatives, e.g. Dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.

    Bevorzugte Polyalkylenterephthalate lassen sich aus Terephthalsäuren (oder ihren reaktionsfähigen Derivaten) und aliphatischen und cycloaliphatischen Diolen mit 2 bis 10 C-Atomen nach bekannten Methoden herstellen (Kunststoff-Handbuch), Band VIII, S. 695 ff, Carl Hanser Verlag, München 1973).Preferred polyalkylene terephthalates can be obtained from terephthalic acids (or their reactive derivatives) and aliphatic and cycloaliphatic diols with 2 produce up to 10 carbon atoms using known methods (plastics manual), Volume VIII, p. 695 ff, Carl Hanser Verlag, Munich 1973).

    Bevorzugte Polyalkylenterephthalate enthalten 80 bis 100, vorzugsweise 90 bis 100 Mol-%, bezogen auf die Dicarbonsäurekomponente, Terephthalsäurereste und 80 bis 100, vorzugsweise 90 bis 100 Mol-%, bezogen auf die Diolkomponente, Ethylenglykol und/oder Butandiol-1,4-Reste. Neben Terephthalsäureresten sind 0 bis 20 Mol-% Reste anderer aromatischer Dicarbonsäuren mit 8 bis 14 C-Atomen oder aliphatischer Dicarbonsäuren mit 4 bis 12 C-Atomen enthalten, wie Reste von Phthalsäure, Isophthalsäure, Naphthalin-2,6-dicarbonsäure, 4,4'-Diphenyldicarbonsäure, Bernstein-, Adipin-, Sebacin-, Azelain- oder Cyclohexandiessigsäure. Neben Ethylenglykol- und/oder Butandiol-1,4-Resten sind 0 bis 20 Mol-% anderer aliphatischer Diole mit 3 bis 12 C-Atomen oder cycloaliphatischer Diole mit 6 bis 12 C-Atomen enthalten, z.B. Reste von Pentandiol-1,5, Hexandiol-1,6, Cyclohexandimethanol-1,4, 3-Methylpentandiol-1,3 und -1,6, 2-Ethylhexandiol-1,3, 2,2-Diethylpropandiol-1,3, Hexandiol-2,5, 1-4-Di(β-hydroxyethoxyphenyl)-propan, 2,4-Dihydroxy-1,1,3,3-tetramethylcyclobutan, 2,2-Bis-(3-β-hydroxyethoxyphenyl)-propan und 2,2-Bis-(4-hydroxypropoxyphenyl)-propan (DE-OS 2 407 647, 2 407 776, 2 715 932).Preferred polyalkylene terephthalates contain 80 to 100, preferably 90 to 100 mol%, based on the dicarboxylic acid component, terephthalic acid residues and 80 to 100, preferably 90 to 100 mol%, based on the diol component, Ethylene glycol and / or 1,4-butanediol residues. In addition to terephthalic acid residues, 0 up to 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or contain aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, Succinic, adipic, sebacic, azelaic or cyclohexanediacetic acid. Next Ethylene glycol and / or 1,4-butanediol residues are 0 to 20 mol% of other aliphatic Diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 12 carbon atoms included, e.g. Residues of pentanediol-1,5, hexanediol-1,6, cyclohexanedimethanol-1,4, 3-methylpentanediol-1,3 and -1,6, 2-ethylhexanediol-1,3, 2,2-diethylpropanediol-1,3, Hexanediol-2,5,1-4-di (β-hydroxyethoxyphenyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis- (3-β-hydroxyethoxyphenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-OS 2 407 647, 2 407 776, 2 715 932).

    Die Polyalkylenterephthalate können durch Einbau relativ kleiner Mengen 3- oder 4-wertiger Alkohole oder 3- oder 4-basiger Carbonsäuren, wie sie in DE-OS 1 900 270 und US-PS 3 692 744 beschrieben sind, verzweigt werden. Beispiele bevorzugter Verzweigungsmittel sind Trimesinsäure, Trimellithsäure, Trimethylolethan und -propan und Pentraerythrit. Es ist ratsam, nicht mehr als 1 Mol-% des Verzweigungsmittels, bezogen auf die Säurekomponente, zu verwenden. The polyalkylene terephthalates can be 3- or by incorporating relatively small amounts 4-valent alcohols or 3- or 4-based carboxylic acids, as described in DE-OS 1 900 270 and US Pat. No. 3,692,744 are described. Examples of preferred branching agents are trimesic acid, trimellitic acid, Trimethylolethane and propane and pentraerythritol. It is advisable not to exceed 1 mol% of the branching agent, based on the acid component use.

    Besonders bevorzugt sind Polyalkylenterephthalate, die allein aus Terephthalsäure (oder deren reaktionsfähigen Derivaten, z.B. deren Dialkylestern) und Ethandiol und/oder Butandiol-1,4 hergestellt worden sind, sowie deren Mischungen.Polyalkylene terephthalates which consist solely of terephthalic acid are particularly preferred (or their reactive derivatives, e.g. their dialkyl esters) and ethanediol and / or 1,4-butanediol have been prepared, and mixtures thereof.

    Bevorzugte Polyalkylenterephthalate sind auch Copolyester, die aus mindestens zwei der obengenannten Diole hergestellt sind; besonders bevorzugte Copolyester sind Poly-(ethylenglykol/butandiol-1,4)-terephthalate. In den Copolyestern können die verschiedenen Diolreste in Form von Blöcken oder statistisch verteilt vorliegen.Preferred polyalkylene terephthalates are also copolyesters which consist of at least two of the above diols are prepared; particularly preferred copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates. Can in the copolyesters the various diol residues in the form of blocks or statistically distributed available.

    Die Polyalkylenterephthalate besitzen im allgemeinen eine Intrinsic-Viskosität von 0,4 bis 1,4 dl/g, vorzugsweise 0,5 bis 1,3 dl/g, insbesondere 0,6 bis 1,2 dl/g, jeweils gemessen in Phenol/o-Dichlorbenzol (1:1 Gew.-Tl.) bei 25°C.The polyalkylene terephthalates generally have an intrinsic viscosity of 0.4 to 1.4 dl / g, preferably 0.5 to 1.3 dl / g, in particular 0.6 to 1.2 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 part by weight) at 25 ° C.

    Feinstteilige anorganische Materialien BVery fine inorganic materials B

    Komponente B umfaßt feinstteilige anorganische Materialien aus BaSO4, TiN, TiO2, TaC, SiC, WC, WO3, ZrO2, Eisenoxide. Mischungen und dotierte Verbindungen sind ebenfalls verwendbar. Besonders bevorzugt sind BaSO4, TiO2, ZrO2, ganz besonders bevorzugt ist BaSO4.Component B comprises very finely divided inorganic materials made of BaSO 4 , TiN, TiO 2 , TaC, SiC, WC, WO 3 , ZrO 2 , iron oxides. Mixtures and doped compounds can also be used. BaSO 4 , TiO 2 , ZrO 2 are particularly preferred, BaSO 4 is very particularly preferred.

    Die feinstteiligen anorganischen Materialien können nach üblichen Verfahren in die thermoplastischen Kunststoffe A eingearbeitet werden, beispielsweise durch direktes Kneten oder Extrudieren von Kunststoff A und den feinstteiligen anorganischen Pulvern B. Bevorzugte Verfahren stellen die Herstellung eines Masterbatch, z.B. in Flammschutzadditiven und anderen Additiven, Monomeren oder Lösungsmitteln, oder die Cofällung einer wäßrigen Emulsion und den feinstteiligen anorganischen Materialien dar.The very finely divided inorganic materials can be used in conventional processes the thermoplastics A are incorporated, for example by direct kneading or extrusion of plastic A and the finely divided inorganic powders B. Preferred methods are the production of a Masterbatch, e.g. in flame retardant additives and other additives, monomers or solvents, or the co-precipitation of an aqueous emulsion and the finely divided inorganic materials.

    Erfindungsgemäß ist die Herstellung von feinstteiligen anorganischen Materialien in Gegenwart von wäßrigen Polymersystemen, z.B. ABS-Latices. Damit gelingt ohne separate Aufarbeitung der feinstteiligen anorganischen Materialien die Einarbeitung in die thermoplastischen Formmassen.According to the invention, the production of very finely divided inorganic materials in the presence of aqueous polymer systems, e.g. ABS-latexes. It works Incorporation without separate processing of the finely divided inorganic materials into the thermoplastic molding compounds.

    Die durchschnittlichen Teilchendurchmesser (d50) sind 0,1 bis 100 nm, bevorzugt 0,1 bis 50 nm, besonders bevorzugt 0,1 bis 30 nm.The average particle diameter (d 50 ) is 0.1 to 100 nm, preferably 0.1 to 50 nm, particularly preferably 0.1 to 30 nm.

    Teilchengröße und Teilchendurchmesser bedeutet immer den mittleren Teilchendurchmesser d50. Dies kann z.B. durch Ultrazentrifugenmessungen nach W. Scholtan et al., Kolloid-Z und Z. Polymere 250 (1972), S. 782 bis 796 bestimmt werden (bevorzugt bei Dispersionen) oder durch Transmissionselektronenmirkoskopie TEM) (bevorzugt bei thermoplastischen Formmassen).Particle size and particle diameter always mean the average particle diameter d 50 . This can be determined, for example, by ultracentrifuge measurements according to W. Scholtan et al., Kolloid-Z and Z. Polymer 250 (1972), pp. 782 to 796 (preferably in the case of dispersions) or by transmission electron microscopy (TEM) (preferably in the case of thermoplastic molding compositions).

    Die erfindungsgemäßen Formmassen enthalten mindestens ein thermoplastisches Polymerisat auf Basis von ungesättigten Monomeren enthaltend mindestens ein Styrol(derivat) oder mindestens ein Polykondensat von bifunktionellen reaktiven Verbindungen oder Mischungen daraus, und mindestens ein anorganisches Material mit einem mittleren Teilchendurchmesser (d50) von 0,1 bis 100 nm, bevorzugt 1 bis 50 nm, besonders bevorzugt 1 bis 30 nm. Bevorzugte Mengen der anorganischen feinstteiligen Materialien sind 0,1 bis 50 Gew.-%, besonders bevorzugt 0,1 bis 30 Gew.-%, ganz besonders bevorzugt 0,1 bis 10 Gew.-% (bezogen auf thermoplastische Formmassen A).The molding compositions according to the invention contain at least one thermoplastic polymer based on unsaturated monomers containing at least one styrene (derivative) or at least one polycondensate of bifunctional reactive compounds or mixtures thereof, and at least one inorganic material with an average particle diameter (d 50 ) of 0.1 to 100 nm, preferably 1 to 50 nm, particularly preferably 1 to 30 nm. Preferred amounts of the inorganic very finely divided materials are 0.1 to 50% by weight, particularly preferably 0.1 to 30% by weight, very particularly preferably 0, 1 to 10 wt .-% (based on thermoplastic molding compositions A).

    Zur Erhöhung des Röntgenkontrastes sind weiterhin alle üblichen Füllstoffe, z.B. Pigmente, Farbstoffe, Fasern geeignet, die Elemente enthalten, deren Ordnungszahl über denen des Elementes mit der höchsten Ordnungszahl im eingesetzten Kunststoff liegt und deren mittlerer Teilchendurchmesser im erfindungsgemäßen Bereich liegt.To increase the x-ray contrast, all usual fillers, e.g. Suitable pigments, dyes, fibers that contain elements, their atomic number above that of the element with the highest atomic number in the inserted Plastic is and their average particle diameter in the invention Area.

    Neben den erfindungsgemäßen Verbindungen können die Formmassen übliche Zusätze wie Pigmente, Füllstoffe, Stabilisatoren, Antistatika, Gleitmittel, Entformungsmittel, Flammschutzmittel enthalten, sofern sie die Zähigkeit nicht reduzieren. In addition to the compounds according to the invention, the molding compositions can be customary Additives such as pigments, fillers, stabilizers, antistatic agents, lubricants, mold release agents, Contain flame retardants, provided they do not reduce the toughness.

    Herstellung und Prüfung der erfindungsgemäßen FormmassenProduction and testing of the molding compositions according to the invention Beispiel 1 (Vergleich)Example 1 (comparison)

    Handelsübliches BaSO4 (Barifine BF20, Nordmann+Rassmann, Teilchengröße ca. 25 µm) wird in ein Acrylnitril-Butadien-Styrol-Copolymer (ABS) eingearbeitet, indem das Polymer in Gegenwart von BaSO4 aufgeschmolzen wird, die Komponenten gemischt und direkt abgespritzt werden. Die durchschnittliche Teilchengröße des BaSO4 im Polymer (Bildauswertung aus Transmissionselektronenmikroskopie) beträgt ca. 25 µm, die BaSO4-Konzentration beträgt 10 Gew.-% (Polymer P1).Commercial BaSO 4 (Barifine BF20, Nordmann + Rassmann, particle size approx. 25 µm) is incorporated into an acrylonitrile-butadiene-styrene copolymer (ABS) by melting the polymer in the presence of BaSO 4, mixing the components and spraying them off directly , The average particle size of the BaSO 4 in the polymer (image evaluation from transmission electron microscopy) is approx. 25 µm, the BaSO 4 concentration is 10% by weight (polymer P1).

    Die Herstellung von Spritzgußteilen für die Ausprüfung der Eigenschaften an den Polymeren P1, P2, P2A, P3, P4, P5 und P6 erfolgt durch Vormischen der Komponenten, ("Dry Blending") und anschließender Direktverarbeitung. Dazu wird das Gemisch aufgeschmolzen und direkt abgespritzt. Die Verarbeitungstemperatur beträgt 250°C, die Werkzeugtemperatur 70°C.The production of injection molded parts for testing the properties of the Polymers P1, P2, P2A, P3, P4, P5 and P6 are made by premixing the components, ("Dry Blending") and subsequent direct processing. This will be The mixture melted and sprayed directly. The processing temperature is 250 ° C, the tool temperature is 70 ° C.

    Beispiel 2 (Erfindungsgemäß)Example 2

    Feinstteiliges BaSO4 wird in-situ in Gegenwart eines SAN-Latex hergestellt. Dazu werden 5,261 kg SAN-Latex (Feststoff: 43,55 Gew.-%) vorgelegt und 22,2 g Natriumdodecylsulfat (SDS) in 380 g Wasser innerhalb von 50 min zugetropft. Anschließend werden 244,7 g Na2SO4 in 4 600 g Wasser innerhalb von 2,5 h zugetropft. Anschließend erfolgt die Zugabe von 367 g Ba(Acetat)2 in 4 000 g Wasser über 2,5 h bei einer Rührgeschwindigkeit von 430 U/min. Barium liegt gegenüber Sulfat im Unterschuß vor.Very fine BaSO 4 is produced in-situ in the presence of a SAN latex. For this purpose, 5.261 kg of SAN latex (solid: 43.55% by weight) are introduced and 22.2 g of sodium dodecyl sulfate (SDS) in 380 g of water are added dropwise within 50 minutes. 244.7 g of Na 2 SO 4 in 4,600 g of water are then added dropwise over the course of 2.5 h. 367 g of Ba (acetate) 2 in 4,000 g of water are then added over a period of 2.5 hours at a stirring speed of 430 rpm. Barium is deficient compared to sulfate.

    Anschließend wird der Latex gefällt. Dazu wird eine Fällflotte bestehend aus 11,5 Wasser, 115 ml konz. Essigsäure und 230 g Bittersalz (MgSO4*7H2O) vorgelegt. Die Flotte wird auf 95°C aufgeheizt. Unter Rühren wird die Dispersion zugegeben, auf 100°C aufgeheizt und 10 min bei dieser Temperatur belassen. Die Fällung wird durch Wasserzugabe abgekühlt und auf einem Planfilter sulfatfrei gewaschen. Das entstandene Pulver wird bei 70°C getrocknet (Polymer P2). Der mittlere Teilchendurchmesser des BaSO4 im Polymer (Bildauswertung aus Transmissionselektronenmikroskopie) beträgt ca. 40 nm. Then the latex is precipitated. A precipitation liquor consisting of 11.5 water, 115 ml conc. Acetic acid and 230 g of Epsom salt (MgSO 4 * 7H 2 O) submitted. The liquor is heated to 95 ° C. The dispersion is added with stirring, heated to 100 ° C. and left at this temperature for 10 min. The precipitate is cooled by adding water and washed sulfate-free on a plan filter. The resulting powder is dried at 70 ° C (polymer P2). The average particle diameter of BaSO 4 in the polymer (image evaluation from transmission electron microscopy) is approx. 40 nm.

    Das Polymer P2 wird mit einem ABS-Pfropfpulver vermischt und abgespritzt. Der BaSO4-Anteil im Endprodukt beträgt 10 Gew.-%. Die durchschnittliche Partikelgröße des BaSO4 im Polymer (Bildauswertung aus Transmissionselektronenmikroskopie) beträgt ca. 40 nm (Polymer P2A).The polymer P2 is mixed with an ABS graft powder and sprayed off. The BaSO 4 content in the end product is 10% by weight. The average particle size of BaSO 4 in the polymer (image evaluation from transmission electron microscopy) is approx. 40 nm (polymer P2A).

    Beispiel 3 (Vergleich)Example 3 (comparison)

    Handelsübliches BaSO4 (Barifine BF 20, Nordmann+Rassmann, mittlerer Teilchendurchmesser ca. 25 µm) wird in ein Acrylnitril-Styrol-Copolymer (SAN) eingearbeitet, indem das Polymer in Gegenwart von BaSO4 aufgeschmolzen wird, die Komponenten gemischt und direkt abgespritzt werden. Der mittlere Teilchendurchmesser des BaSO4 im Polymer (Bildauswertung aus Transmissionselektronenmikroskopie) beträgt ca. 25 µm, die BaSO4-Konzentration beträgt 10 Gew.-% (Polymer P3). Die Polymermatrix ist ohne BaSO4 transparent.Commercial BaSO 4 (Barifine BF 20, Nordmann + Rassmann, average particle diameter approx. 25 µm) is incorporated into an acrylonitrile-styrene copolymer (SAN) by melting the polymer in the presence of BaSO 4, mixing the components and spraying them off directly , The average particle diameter of the BaSO 4 in the polymer (image evaluation from transmission electron microscopy) is approx. 25 µm, the BaSO 4 concentration is 10% by weight (polymer P3). The polymer matrix is transparent without BaSO 4 .

    Beispiel 4 (erfindungsgemäß)Example 4

    Das in Beispiel 2 hergestellte Pulver (Polymer P2), bestehend aus feinstteiligem BaSO4 in gefälltem und getrocknetem SAN-Latex, wird nicht wie in Beispiel 2 mit einem ABS-Pfropfpulver vermischt, sondern mit SAN (Polymer P4). Der mittlere Teilchendurchmesser des BaSO4 im Polymer (Bildauswertung aus Transmissionselektronenmikroskopie) beträgt ca. 40 nm, die BaSO4-Konzentration beträgt 10 Gew.-%. Die Polymermatrix ist ohne BaSO4 transparent.The powder (polymer P2) produced in example 2, consisting of very fine BaSO 4 in precipitated and dried SAN latex, is not mixed with an ABS graft powder as in example 2, but with SAN (polymer P4). The average particle diameter of the BaSO 4 in the polymer (image evaluation from transmission electron microscopy) is approx. 40 nm, the BaSO 4 concentration is 10% by weight. The polymer matrix is transparent without BaSO 4 .

    Beispiel 5 (Vergleich)Example 5 (comparison)

    SAN wird mit ABS-Pfropfpulver gemischt (Polymer P5) und verspritzt.SAN is mixed with ABS graft powder (polymer P5) and sprayed.

    Beispiel 6 (Vergleich)Example 6 (comparison) SAN wird zu Vergleichszwecken abgespritzt (Polymer P6)SAN is hosed down for comparison (polymer P6)

    Die Polymerzusammensetzung der Polymerisate P1, P2A und P5 ist identisch und hat folgende Zusammensetzung:The polymer composition of the polymers P1, P2A and P5 is identical and has the following composition:

    Die Acrylnitril-Butadien-Styrol-Polymerisate (ABS) bestehen aus 63,64 Gew.-% SAN-Harz und 36,36 Gew.-% ABS-Propfpulver. SAN ist ein thermoplastisches Harz bestehend aus 28 Gew.-% Acrylnitril und 72 Gew.-% Styrol. SAN kann durch Emulsionspolymerisation (SAN-Latex) oder Masseverfahren hergestellt werden. Die Viskosität des SAN-Harzes wurde durch den L-Wert charakterisiert (L-Wert = ηspez./C bei c = 5 g/l in DMF bei 25°C). Der L-Wert des eingesetzten SAN-Harzes ist 60.The acrylonitrile-butadiene-styrene polymers (ABS) consist of 63.64% by weight SAN resin and 36.36% by weight ABS graft powder. SAN is a thermoplastic resin consisting of 28% by weight acrylonitrile and 72% by weight styrene. SAN can be made by emulsion polymerization (SAN latex) or bulk process. The viscosity of the SAN resin was characterized by the L value (L value = η spec./C at c = 5 g / l in DMF at 25 ° C). The L value of the SAN resin used is 60.

    ABS-Propfpulver wird durch Emulsionspolymerisation von Styrol und Acrylnitril in Gegenwart einer wäßrigen Polybutadien-Emulsion (Polybutadien-Grundlage) hergestellt. Dabei wird Styrol und Acrylnitril auf die Polybutadien-Teilchen aufgepfropft. Die Pfropfung ist bekanntermaßen nicht vollständig, so daß neben gepfropftem SAN auch freies SAN im ABS-Propfpulver vorliegt. Das ABS-Pfropfpulver besteht aus 55 Gew.-% Polybutadien und 45 Gew.-% SAN (Styrol:Acrylnitril = 72 Gew.-%:28 Gew.-%). Die Partikelgröße der Polybutadien-Grundlage beträgt 0,4 µm.ABS graft powder is made by emulsion polymerization of styrene and acrylonitrile in the presence of an aqueous polybutadiene emulsion (polybutadiene base) manufactured. Styrene and acrylonitrile are applied to the polybutadiene particles grafted. As is known, the grafting is not complete, so that in addition to grafted SAN there is also free SAN in the ABS graft powder. The ABS graft powder consists of 55% by weight of polybutadiene and 45% by weight of SAN (styrene: acrylonitrile = 72% by weight: 28% by weight). The particle size of the polybutadiene base is 0.4 µm.

    Die Polymerzusammensetzung der Polymerisate P3, P4 und P6 ist identisch und hat folgende Zusammensetzung:The polymer composition of the polymers P3, P4 and P6 is identical and has the following composition:

    Das Styrol-Acrylnitril-Polymerisat (SAN) stellt ein transparentes, thermoplastisches Harz dar, bestehend aus 28 Gew.-% Acrylnitril und 72 Gew.-% Styrol. SAN kann durch Emulsionspolymerisation (SAN-Latex) oder Masseverfaharen hergestellt werden. Die Viskosität des SAN-Harzes wurde durch den L-Wert charakterisiert (L-Wert = ηspez./C bei c = 5 G/l in DMF bei 25°C). Der L-Wert des eingesetzten SAN-Harzes ist 60.The styrene-acrylonitrile polymer (SAN) is a transparent, thermoplastic resin consisting of 28% by weight of acrylonitrile and 72% by weight of styrene. SAN can be made by emulsion polymerisation (SAN latex) or mass processing. The viscosity of the SAN resin was characterized by the L value (L value = η spec./C at c = 5 G / l in DMF at 25 ° C). The L value of the SAN resin used is 60.

    Vergleich von Polymer P1, P5 und P2AComparison of polymer P1, P5 and P2A

    Zum Vergleich der Eigenschaften von konventionellem BaSO4 und feinstteiligem BaSO4 in thermoplastischen Formmassen werden die thermoplastischen Formmassen abgespritzt und folgende Untersuchungen durchgeführt:To compare the properties of conventional BaSO 4 and very fine-particle BaSO 4 in thermoplastic molding compounds, the thermoplastic molding compounds are sprayed off and the following tests are carried out:

    a) Kerbschlagzähigkeit (ak)a) impact strength (a k )

    Durch Spritzgießen werden Stäbe der Abmessung 80 x 10 x 4 mm3 hergestellt, an denen die Kerbschlagzähigkeit bei Raumtemperatur nach der Methode ISO 180 1 A gemessen wird. Injection molding is used to produce rods measuring 80 x 10 x 4 mm 3 , on which the notched impact strength is measured at room temperature using the ISO 180 1 A method.

    b) Zug-E-Modulb) tensile modulus

    Durch Spritzgießen werden Schulterstäbe ("Zugstab Nr. 3") hergestellt, an denen Zugversuche nach DIN 53 455 mit E-Modulbestimmung nach DIN 53 457 durchgeführt werden.Shoulder bars ("tension bar No. 3") are produced by injection molding, on which Tensile tests according to DIN 53 455 with elastic modulus determination according to DIN 53 457 be performed.

    c) Wärmeformbeständigkeit (Vicat B 120)c) heat resistance (Vicat B 120)

    Durch Spritzgießen werden Stäbe der Abmessung 80 x 10 x 4 mm3 hergestellt, an denen die Vicat-Erweichungstemperatur (VST) nach ISO 306 bestimmt wird.Injection molding is used to produce rods measuring 80 x 10 x 4 mm 3 , on which the Vicat softening temperature (VST) is determined in accordance with ISO 306.

    d) ESC-Verhalten (Benzinbeständigkeit)d) ESC behavior (petrol resistance)

    Die Benzinbeständigkeit (Spannungsrißverhalten) wird an den Flachstäben 80 x 10 x 4 mm3 gemäß DIN 53 449/3 untersucht. Als Kraftstoffsimulanz wurde eine Mischung aus 50 Gew.-% Toluol und 50 Gew.-% Isooctan verwendet. Die Probekörper wurden mittels einer Kreisbogenschablone vorgedehnt und 5 Minuten bei 23°C im Kraftstoffsimulanz gelagert. Das Spannungsrißverhalten wurde über die Rißbildung bzw. den Bruch beurteilt. Die Vordehnung, bei der nach 5 Minuten ein Bruch auftritt, ist in folgender Tabelle dargestellt.The gasoline resistance (stress crack behavior) is examined on the flat bars 80 x 10 x 4 mm 3 according to DIN 53 449/3. A mixture of 50% by weight of toluene and 50% by weight of isooctane was used as fuel simulant. The test specimens were pre-stretched using a circular template and stored in the fuel simulator for 5 minutes at 23 ° C. The stress crack behavior was assessed via the crack formation or the break. The pre-stretch, which breaks after 5 minutes, is shown in the following table.

    Die Ergebnisse der Untersuchungen sind in folgender Tabelle zusammengefaßt: Polymer BaSO4 [Gew.-%] Feinstteiliges BaSO4 [Gew.-%] ak [kJ/m2] E-Modul [N/mm2] Vicat B 120 [°C] Vordehnung bis zum Bruch P5 - - 19 2330 99 0,6 P1 10 - 4 2560 100 0,4 P2A (erfindungsgemäß) - 10 12 2500 103 2,4 The results of the tests are summarized in the following table: polymer BaSO 4 [% by weight] Very fine BaSO 4 [% by weight] ak [kJ / m 2 ] Modulus of elasticity [N / mm 2 ] Vicat B 120 [° C] Pre-stretch to break P5 - - 19 2330 99 0.6 P1 10 - 4 2560 100 0.4 P2A (according to the invention) - 10 12 2500 103 2.4

    Die Kerbschlagzähigkeit zeigt bei 10 Gew.-% feinstteiligem BaSO4 ein für ABS akzeptables Niveau, während die Kerbschlagzähigkeit mit 10 Gew.-% handelsüblichem BaSO4 drastisch abfällt (Abnahme auf ca. 1/5 des Ausgangsniveaus). Bereits geringe Mengen des handelsüblichen BaSO4 (1,5 Gew.-%) führen zu einem Zähigkeitsabfall auf ca. die Hälfte des Ausgangsniveaus.The notched impact strength at 10% by weight of finely divided BaSO 4 shows an acceptable level for ABS, while the notched impact strength drops drastically with 10% by weight of commercially available BaSO 4 (decrease to approx. 1/5 of the initial level). Even small amounts of the commercially available BaSO 4 (1.5% by weight) lead to a drop in toughness to approximately half of the initial level.

    Die Benzinbeständigkeit, ausgedrückt in der Randfaserdehnung bis zum Bruch, ist deutlich verbessert beim Zusatz von feinstteiligem BaSO4. Der Zusatz von konventionellem BaSO4 verbessert diese Eigenschaft nicht.The gasoline resistance, expressed in the edge fiber stretching to breakage, is significantly improved when adding finely divided BaSO 4 . The addition of conventional BaSO 4 does not improve this property.

    Polymer P5 zeigt im Röntgenexperiment keinen Röntgenkontrast. Polymer P1 zeigt unter den gleichen Bedingungen einen deutlichen, etwas diffusen Röntgenkontrast, während das erfindungsgemäße Polymer P2A unter gleichen Bedingungen einen deutlichen, scharfen Röntgenkontrast zeigt.Polymer P5 shows no X-ray contrast in the X-ray experiment. Polymer P1 shows a clear, somewhat diffuse X-ray contrast under the same conditions, while the polymer P2A according to the invention under the same conditions shows a clear, sharp X-ray contrast.

    Vergleich von P4, P3 und P6Comparison of P4, P3 and P6

    Verglichen wird die Transparenz von SAN, einem transparenten Polymer, nach Zusatz von handelsüblichem BaSO4 und feinstteiligem BaSO4. Gemessen wird die Trübung nach ASTM D 1003.
    Die Stärke der Probenkörper beträgt 2 mm.
    Die Ergebnisse der Untersuchungen sind in folgender Tabelle zusammengefaßt: Polymer BaSO4 [Gew.-%] Feinstteiliges BaSO4 [Gew.-%] Trübung [%] P6 - - 34 P3 10 - 89 P4 (erfindungsgemäß) - 10 56     The transparency of SAN, a transparent polymer, is compared after the addition of commercially available BaSO 4 and finely divided BaSO 4 . The turbidity is measured in accordance with ASTM D 1003.
    The thickness of the test specimen is 2 mm.
    The results of the tests are summarized in the following table: polymer BaSO 4 [% by weight] Very fine BaSO 4 [% by weight] Turbidity [%] P6 - - 34 P3 10 - 89 P4 (according to the invention) - 10 56

    Claims (12)

    1. Thermoplastic moulding compositions substantially consisting of
      A. a thermoplastic polymer selected from
      A.1) copolymers formed firstly from styrene, α-methylstyrene, a styrene comprising a substituted nucleus or mixtures thereof (A.1.1), and secondly from acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleinimide or mixtures thereof (A.1.2),
      A.2) a graft polymer of
      A.2.1 5 to 95 parts by weight of a mixture of
      A.2.1.1 50 to 95 parts by weight of styrene, α-methylstyrene, styrenes comprising halogen- or methyl-substituted nuclei, methyl methacrylate, or mixtures of said compounds, and
      A.2.1.2 5 to 50 parts by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, C1-C4 alkyl- or phenyl-N-substituted maleinimides or mixtures of said compounds, on
      A.2.2 5 to 95 parts by weight of a rubber polymer having a glass transition temperature of -10°C,
      or mixtures of A.1) and A.2) and optionally of a thermoplastic polycarbonate, and
      B) 0.1 to 50 % by weight (with respect to A) of an inorganic substance with an average particle diameter of 0.1 to 100 nm,
      selected from BaSO4, TiN, TiO2, TaC, SiC, WC, WO3, ZrO2 and iron oxides, and mixtures thereof or of doped compounds.
    2. Thermoplastic moulding compositions according to claim 1, wherein A.1) is a copolymer of 50 - 98 % by weight of styrene, α-methylstyrene, styrene comprising a substituted nucleus, methyl methacrylate, or mixtures thereof, and 50 to 2 % by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, an N-substituted maleic imide or mixtures thereof.
    3. A moulding composition according to claims 1 or 2, wherein rubber polymer A.2.2 is selected from polybutadiene, butadiene/styrene copolymers, acrylate rubbers and silicone rubbers.
    4. A moulding composition according to claims 1 to 3, containing 0.1 to 30 % by weight of component B with respect to A).
    5. A moulding composition according to claims 1 to 4, wherein the average particle diameter of component B) is 0.1 to 50 nm.
    6. A moulding composition according to claim 5, wherein the average particle diameter is 0.1 to 30 nm.
    7. A moulding composition according to claims 1 to 6, wherein component B) is selected from barium sulphate, titanium dioxide or zirconium dioxide.
    8. Thermoplastic moulding compositions according to claims 1 to 7, wherein B) is BaSO4.
    9. Thermoplastic moulding compositions according to claim 1, wherein A) is a mixture of a thermoplastic polycarbonate, a copolymer and a graft polymer of resin-forming vinyl monomers on a rubber.
    10. A process for producing thermoplastic moulding compositions according to claim 1, characterised in that the inorganic material, which has an average particle diameter of 0.1 to 100 nm, is produced in the presence of a latex of the thermoplastic polymer and is then worked up jointly.
    11. The use of superfine inorganic substances as defined by B) in claim 1 for increasing the X-ray contrast of thermoplastic moulding compositions comprising A) and B).
    12. Thermoplastic moulding compositions according to claims 1 to 10, containing customary additives.
    EP96118830A 1995-12-05 1996-11-25 Thermoplastic compositions with improved X-ray contrast Expired - Lifetime EP0783019B1 (en)

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    DE19545289A DE19545289A1 (en) 1995-12-05 1995-12-05 Thermoplastic materials with improved X-ray contrast
    DE19545289 1995-12-05

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    DE19545289A1 (en) 1997-06-12

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